p, p&#39;-methylene bis



UNITED STATES PATENT OFFICE p,p-METHYLENE BIS (BENZENE SULFONYL HYDRAZIDE) Byron A. Hunter, Oxford, COlllL, assignor to United States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing. Application May 14, 1952, Serial No. 287,798

1 Claim. (Cl. 260-556) 1 2 This invention resides in my discovery of p,p'- Percent chlorine calculated for C13H1tO4SzC12: methylene blS (benzene sulfonyl hydrazide) as a 19.45%. Percent chlorine found: 19.96%, 20.06%. new and useful composition of matter. This sub- Percent sulfur calculated for CnHmO-iSzCh:

stance is a white, crystalline solid which melts 17.53%. Percent sulfur found: 17.37%, 17.34%, with decomposition at l64-164.5 C. Nitrogen 5 17.31%.

gas is a product of the decomposition. When it t is incorporated in rubber and subjected to normal Preparatwn of Z g ms (benzene curing temperatures the compound acts as a very fmw y mm 8) efficient blowing agent and is capable of produc- Thirteen a d One-half grams (004 111018) of ing a light colored non-odorous cellular product 10 D,p'-methylene bis (benzene sulfonyl chloride) possessing a fine and uniform cell structure which (M. P. 120-122" C.) was placed in a 500 0Q 3-1186}! is very desirable. Blown organic plastics of exflask q pp t e addition funnel, and cellent quality can also be made by using this thermometer. Eethyl alcohol (150 cc.) was added chemical as a blowing agent. and the mixture was stirred as 5.5 g. (0.16 moles) p,p'-Methylene bis (benzene sulfonyl hydraof 95% hydrazine was gradually added. The zide) may be prepared from diphenyl methane by m ur as p near y means Of a 0001- first forming the disulfonyl chloride by treatment ing bath. Stirring was continued for two hours with chlorosulfonic acid and reacting the disulafter the addition of the hydrazine was comfonyl chloride so produced with hydrazine. The pleted. The reaction mixture was then poured transformations are represented in the following 20 into 1000 cc. of cold water and the resulting preequations: cipitate was filtered and dried. The crude product weighed 12.9 grams (97.7% of theory) and @cmO 401801011 melted with decomposition at 152 3 c. The material was purified by dissolving in dilute sodium hydroxide solution, filtering from a small amount OISWOCEOSOQm ZHCI of insolubles and reprecipitating by acidification with dilute acetic acid. This solution in CEOZQOHZOSOHH QEHNNH2 caustic and reprecipitation with acid was repeated once more and finally the product was re- H H crystallized from hot distilled water. The result- 'O Q ing white needles melted with decomposition at 164-1645 C. The following analyses agree very There now follows a description of the prepara- 1 th c 10 1 t d lens bis tion of the disulfonyl chloride and of p,px i gi fi g g y methylene bis (benzene sulfonyl hydrazide' Percent sulfur calculated for C13H1604S2N41 17.98%. Percent sulfur found: 17.97% 18.05%. Pr 1? th I b b e epam um iufio r zyl zilo i f is amen Percent carbon calculated for C13H1sO4S2N4: 43.81%. Percent carbon found: 43.54%, 43.39%. Dlphenyl methane was reacted with chloro' Percent hydrogen calculated for C1sH1eO4S2N4:

sulfonic acid as follows: Eighty-four grams (0.5 451% Percent hydrogen f und: 437%, 4.19% mole) of methane Was heated to 70 Co Having thus described my invention what I A fairly rapid addition of 349-5 grams (3 moles) claim and desire to protect by Letters Patent is: of chlorosulfonic acid was made keeping the tem- AS a new chemical compound. th 1 perature between 60 and 80 C. After the addibis (benzene sulfonyl hydrazide) tion was complete the mixture was cooled to room temperature and stirred for three hours. The BYR N A. HUNTER. mix was quenched in cold water and the resulting precipitate was filtered, washed with water and dried. The crude product weighed 118.5 grams References clted m the me of thls patent (64.3% yield). This material was recrystallized UNITED STATES PATENTS from chloroform, from ethyl acetate, and again v Number Name Date from chloroform, whereupon, the material melted at 120-122 C. A portion of the material was re- 2552065 Schoene May 1951 crystallized twice more from chloroform, using Dicalite (diatomaceous earth) as a decolorizing FQREIGN PATENTS agent. The product melted at 124 C., in agree- Number Country Date ment with the value reported by Lapworth (J. 9 1. 0 France Oct. 23, 1944 Chem. Soc. 73, 408 (1898)). The following analyses are in very good agreement with those OTHER REFERENCES calculated for p,p'-methylene bis (benzene sul- Hunter et 9.1., India Rubber World vol. 123, tony! chloride), issue 5,1). 577,Feb, 1951. 

